Treating liquid partial oxidation products



herein relate tofractionating a partial oxidation Patented June 1937 PATENT? OFFICE TREATING LIQUID P PxonUo'rs TIAL OXIDATION Joseph Hidy James, Pittsburgh, Pa., assignor to Clarence P. Byrnes, trustee, Sewickley, Pa.

No Drawing. Application May 31, 1921,

Serial No.

18 Claims. (or. 196-142) In several copending applications, I have de-= scribed my process vfor making intermediate or partial oxidation products from hydrocarbons, such as petroleum, petroleum distillates, shale oil and its distillates, etc. These applications mainly relate-to making products, the molecules of which have, as nearly as possible, the same number of carbon atoms as the hydyrocarbons used as raw material. Some of these are Serial Nos. 272,567 filed January 22, 1919; 281,124 filed March 7, 1919;'and 335,939filed November 5, 1919, the latternow being Patent No. 1,759,620 of May 20, 1930'.

As to certain broader claims the inventions product containing oxygen derivatives of hydrocarbon, and also to the product fraction.- As to other claims the present invention is designed to prepare mixtures of oxidation-products and hydrocarbons, the molecules of which have fewer carbon atoms than hydrocarbons of the raw material, although it is not restricted thereto. The process followed out is generally thesame as in the said applications, namely, vapor.- I

5 iatng the hydrocarbon, mixing it with air or an oxygen containing gas, and in some cases, a diluent, such as steam, and passingthe vapor phase mixture through a catalytic layer at a temperature between certain defined limits. As stated in said applications, the temperature in the catalytic zone is below that of self-sustained I combustion and preferably below a red heat. Under one form of the present invention, I prefer to use higher temperature conditions than 5 in former types of my process, where the main products were for other than fuel uses. By using a somewhat higher temperature and a higher ratio of air, I not only effect a partialpxidation of the hydrocarbons treated, but in part, decomposition of the oxidation products at the higher temperature, this giving a higher percentage of carbon monoxide and carbon dioxide in the ofitake gases andproducing hydrocarbons of lower carbon content than those of the mixture 5 charged: thermal decomposition takes I place ,to some extent in my process 'for making other-products, but is increased by the higher temperature and higher" air ratio. This thermal if -d omposition of; the oxidation products also 9 results in the formation of oxygen derivatives of lower carbon content than the original hydrocarbons. The temperature'employed may extend from 5 230? C; up to over 400 (3., andpreferably is in percent of'the oil volume was fed'w'lih the oil to liters per} hour and the .air was-distributed to the upper part of this range the air ratio being well beyond the theoretical proportions.

When the process is carried out in this manner, I find that a considerable proportion of the mixture consists of hydrocarbons of lower carbon content, a considerable amount being within the gasoline or motor spirit range, while a larger proportion is within the kerosene range. I preferably fractionally distil the product taking off, first, a lighter fraction such as the gasoline or motor spirit fraction at its usual endpoint, and then at a highertemperature, take a heavier fraction, such as the kerosene product up to its usual end point. The remainder of the product may then be treated for producing lubricants or other industrial products. The motor spirit range at the present time extends to about 225 C., while the kerosene range extends from this point to up to around 309 C.

The liquid fuels thus produced are of better burning quality and more easily ignited than the ordinary hydrocarbon fractions within ,these ranges of distillation, owing to the greater content of oxygen, due to the oxidation process. The motor spirit produced may be employed in all ordinary internal combustion engines and the kerosene product may be employed in many types of internal combustion engines, such as those for tractor use, etc.

The fraction within the ordinary kerosene range may, if desired, be subjected to a second decomposition step-of the usual cracking type. This cracking may be carried'out in the liquid phase at temperatures giving from 100 to 300 pounds per square inch pressure, or in the pressure liquid and vapor phase or in the pressure vapor phase. or the mixture may be cracked by high frequency, high voltage electrical oscillations in the vaporphase or liquid phase or in the combined liquid and vapor phase.

As an example of one type of my process, I employ a fraction of Mexican fuel oil boiling from 300 C. to 360C. This fractionwas subjected to my partial oxidation process in thethree-screen apparatus of my applicatiom-Serial No. 435,355 filed January 6, l92l,now U. S. Patent 2,054,571, using' as a catalyst theblue oxides of molybdenum deposited on asbestos for the catalytic layer; The temperature of vaporizer being about 330 C,,'a'n amount of waterequal'to aboutten 'aid in vaporization. The air used'was 1.5 liters per minute for every 100 cubic centimeters of oil fed per hour. The oil was fed at "the rate or six the three screens, as noted in the above application. The temperature of the three catalytic screens varied from 380 C. to 400 C., during the run, which lasted for three hours.

The condensed, oxidized product was, involume, equal to about 80% of the oil fed. This product contained about 30% by volume of alde- 'hyde fatty acids and 20% by volume of aldehydes fit and aldehyde alcohols, the remaining 50% being made up of other oxygenated bodies, together with hydrocarbons of low molecular weight, resulting from decomposition of oxygenated bodies.

On distillation, .the product gave 12% of a fraction boiling under 200 C. and of a fraction boiling under 300 C. The oxygenated bodies are distributed through the entire range of fractions obtained by fractionally distilling the product. "Q

If a heavy Mexican distillate is used or wax" distillate from the Mid-Continental oils or gas oil. or other byproducts from the Pennsylvania or other oils, or pressure tar (a byproduct from the cracking of oils) I prefer to distil the oxidized product taking the portion about 300 C. or in some cases above 300 C., as the starting point for grease manufacture or lubricating oil manufacture, as described in other co-pending applications, some of which are now patents, includlllg Patents Nos. 1,700,055, 1,700,056, both of January 22, 1929, and 2,054,571 of September 15, 1936. i

The fraction of the oxidized product mixture boiling below either of the above points may, in certain cases, be used as a fuel, without other chemical treatment. This product, because of its oxygenated character, burns more rapidly than ordinary hydrocarbon fractions boiling between the same limits. This fraction or portions of it may be blended to make motor fuels-of high thermal value and ready combustibility. The entire oxidized product mixture under 300 C.,

-may' be used in kerosene tractors or all kerosene engines, where its peculiar chemical character makes it a highly efficient fuel. This total mixture fraction is also specially valuable as a fuel for engines of the Diesel or semi-Diesel type, as the easy oxidizability of the fuel makes it possible to produce the development of power at lower pressures in such types of engine. I

Or as above indicated, it may be separated by distillation into two fractions, one in the gasoline or motor spirit, range and another in the kerosene range. In the latter case, on carrying out one type of cracking or further thermal decom-" position of the kerosene fraction, from 62 to of the total liquid charged was recovered, this giving from around 30 to nearly 50% of a fraction distilling below 200 C. The amount of motor spirit fuel obtained in this cracking of the kerosene fraction will, of course, depend considerably upon the type of cracking process em-. ployed. Y L

. In all cases, that portion of the oxidation product materially distilling above the kerosene range may be, treated for producing industrial products,such as lubricants, greases, etc. In my claims, the words to different degrees of oxidation mean that chemically differing. aliphatic hydrocarbon derivatives are formed in the partial oxidation step: the words oxidized and cracked or "cracked and oxidized" mean thatthe material has been oxidized andcracked, or vice versa, either as successive steps or in the same; step: and the word "hydrocarbons" is used separating. the product into different fractions of different molecular weights, the heavier fraction having a greater percentage of aldehyde fatty.

acids than the other fraction,

2. In the treatment of petroleum hydrocarbons which already contain artificially-introduced chemically-combined. oxygen to different degrees of oxidation in the range from alcohols to oxygenated organic acids some of said different bodies being within the same boiling point range, the step consisting of fractionating the same into fractions of different average molecular weights each containing different bodies within the same boiling point range.

3. As a new composition of matter, 'a liquid fractionatediportion of a partial oxidation product mixture of hydrocarbons'of different molecular weights and containing artificially-introduced chemically-combined oxygen to different degrees of oxidation including alcohols and aldehyde-like bodies of different molecular weights. 2

4. As a new composition of matter, the.thermany-decomposed product of a mixture of partially-oxidized aliphatic hydrocarbons containing alcohols and aldehyde-like bodies.

5. In the treatment of liquid organic bodies of the aliphatic hydrocarbon type, the steps consisting of passing a stream comprising a mixture of said bodies ofdifferent molecular weights and oxygen through a hot reaction zone at a'temperature below a red heat, thereby chemically tying oxygen into the bodies to different degrees of partial oxidation, and recovering and fractioning from the exit stream separate liquid fractions each containing different partially oxidized bodies, some of whichdiiferent bodies are within the same boiling point range, whereby liquid fractions are obtained each of different average molecular weight and each containing several different oxidized bodies within the boiling point range of said fraction and in the range from alcohols to oxygenated organic acids, a lighter fraction containing a less percentage of said acids than a heavier fraction.

6. In the treatment of liquid organic bodies of the aliphatic hydrocarbon type, the steps consisting of passing a stream comprising a mixture of said bodies of different molecular weights and oxygen through a hot reaction zone at a temperature below a red heat, thereby chemically tying oxygen into the bodies to diflerent degrees of partial oxidation, recovering a liquid mixture of different partially oxidized hydrocarbons from the exit stream, and fractioning the same into liquid fractions of different average molecular weights, each containing different bodies in the range from alcohols to oxygenated organic acids, one of said fractions being within the motor spirit range. I v

7. In the treatment of a liquid mixture containing aliphatic hydrocarbons of different mo- 7 I 2,085,499 lecular weights, the steps consisting oi passing a stream of the same and oxygen in contact with a catalyst at a temperature below a red heat, and

recovering and fractioning from the exit stream.

a plurality of fractions each of different average molecular weight and each containing difierent oxidized bodies in oxygenated organic acids.

'8. Inthe treatment of a liquid mixture containing aliphatic hydrocarbons stream of the same and oxygen in contact with a catalyst at a temperature below a red heat, and

' ilecular weights, the

a stream of the same and oxygen in contact with oxidized bodies in oxygenated organic acids and blending a fraction thereof with a liquid hydrocarboncontaining I substantially only hydrogen and carbon.

10. In the treatment oi petroleum hydrocarbons which already contain artificially-introduced chemically-combined oxygen to different-degrees of oxidation in the range irom alcohols to oxy- .genated organic acids, some bodies being within the same boiling point range,

the steps consisting of fractionating the same into averagev molecular weights, 1 each. containing difierent bodies-within thesame I boiling point range, and thermally decomposing a t of said different fractions of different portion of a fraction thereof.

11. In the treatment or .petroleum hydrocarbons which already contain artificially-introduced chemically-combinedoxygen to different degrees from alcohols to oxyof oxidation in the range genated organic acids, some of said different bodies being within the sameboiiing pointrange', the steps consisting of fractionating the-same into fractions ofdifierent average molecular weights, each containing different bodies within the same boiling point range, and thermally decomposing a portion of a fraction thereof under superatmospheric pressure.

12. In the treatment of petroleum hydrocarQ bons which already contain artificially introducedchemically-combined oxygen to diiferent degrees from alcohols to oxyof said different of oxidation in the range genated organic acids, some the range from alcohols 'to g of diflerentmo lecular weights, the steps consisting of passing a each containing diiferent blended with a hydrocarbon.

bodies being within the same boiling point range, the steps consisting of fractionating the same 'into fractions of, different average molecular weights, each containing diiferent bodies within the same boiling point range, and thermally decomposing a portion of a fraction thereof under superatmospheric pressure in the liquid and vapor phase.

13. In the treatment of petroleum hydrocarbons which already contain artificially-introduced chemically combined oxygen to diiferent degrees of oxidation in the range from alcohols to oxygenated organic acids, some of said different bodies being within the fsameboiling point range,

the steps consisting of fractionating the same into fractions of diflerent average molecular weights, each containing different bodies within the same boiling point range, and subjecting a lighter frac- 1 1 tion to thermal decomposition. 14. As a new composition of matter, a liquid mixture of aliphatic. hydrocarbons of diflerent molecular weights, a material percentage of which contains artificially-introduced chemically-combined oxygen to difirent degrees of oxidation in the range from alcohols to oxygenated-organic acids, and also containing cracked hydrocarbons.

15. As a new composition of matter, a liquid fractionated portion of a mixture of aliphatic hydrocarbons of different molecular weights, a

material percentage of which contains a'rtificially'-.

introduced chemicallywombined oxygen to different degrees of oxidation. in the range from alcohols to oxygenatedorganic acids. 1

16. As a new composition. of matter, a liquid mixture of aliphatic hydrocarbons of difierent molecular weights, a material percentage of which contains artificially-introduced chemically-combined oxygen to different degrees of oxidation in the range from alcohols to oxygenated organic acids, and alsocontaining cracked hydrocarbons 17. As a new composition of mattena liquid mixture of aliphatic hydrocarbons of different molecular weights, a'material percentage of which contains artificially-introduced chemically-combined oxygen to different degrees of oxidation in the. range from alcohols to oxygenated organic acids; and also containing cracked hydrocarbons of the character produced by thermal decomposi tion.

lighter fractionated portion of a mixtureof ali- 18. As a .new composition of matter, a liquid phatlc hydrocarbons of diflerent..-molecularweights, a material percentage mixture containing phatiqhydrocarbona a JOSEPH HIDY JAMES.

of which contains artificially-introduced chemically-combined oxygen tddiiferent degrees of oxidation in the range. from alcohols to oxygenated organic acids, said thermally decomposed all-- 

